Bipolar Membranes to Promote Formation of Tight Ice-Like Water for Efficient and Sustainable Water Splitting.

Bipolar membranes (BPMs) have recently received much attention for their potential to improve the water dissociation reaction (WDR) at their junction by utilizing catalysts. Herein, composite catalysts (Fe2 O3 @GO) comprising hematite nanoparticles (α-Fe2 O3 ) grown on 2D graphene oxide (GO) nanosheets are reported, which show unprecedentedly high water dissociation performance in the BPM. Furthermore, new catalytic roles in facilitating WDR at the catalyst-water interface are mechanistically elucidated. It is demonstrated that the partially dissociated bound water, formed by the strongly Lewis-acidic Fe atoms of the Fe2 O3 @GO catalyst, helps the "ice-like water" to become tighter, consequently resulting in weaker intramolecular OH bonds, which reduces activation barriers and thus significantly improves the WDR rate. Notably, Fe2 O3 @GO-incorporated BPM shows an extremely low water dissociation potential (0.89 V), compared to commercially available BPM (BP-1E, 1.13 V) at 100 mA cm-2 , and it is quite close to the theoretical potential required for WDR (0.83 V). This performance reduces the required electrical energy consumption for water splitting by ≈40%, as compared to monopolar (Nafion 212 and Selemion AMV) membranes. These results can provide a new approach for the development of water dissociation catalysts and BPMs for realizing highly efficient water splitting systems.

Formation of Frustrated Lewis Pairs in Ptx -Loaded Zeolite†NaY.

The formation of a frustrated Lewis pair consisting of sodium hydride (Na(+) H(-) ) and a framework-bound hydroxy proton O(H(+) ) is reported upon H2 treatment of zeolite NaY loaded with Pt nanoparticles (Ptx /NaY). Frustrated Lewis pair formation was confirmed using in situ neutron diffraction and spectroscopic measurements. The activity of the intrazeolite NaH as a size-selective catalyst was verified by the efficient esterification of acetaldehyde (a small aldehyde) to form the corresponding ester ethyl acetate, whereas esterification of the larger molecule benzaldehyde was unsuccessful. The frustrated Lewis pair (consisting of Na(+) H(-) and O(H(+) )) generated within zeolite NaY may be a useful catalyst for various catalytic reactions which require both H(-) and H(+) ions, such as catalytic hydrogenation or dehydrogenation of organic compounds and activation of small molecules.

Core-shell strain structure of zeolite microcrystals.

Zeolites are crystalline aluminosilicate minerals featuring a network of 0.3-1.5-nm-wide pores, used in industry as catalysts for hydrocarbon interconversion, ion exchangers, molecular sieves and adsorbents. For improved applications, it is highly useful to study the distribution of internal local strains because they sensitively affect the rates of adsorption and diffusion of guest molecules within zeolites. Here, we report the observation of an unusual triangular deformation field distribution in ZSM-5 zeolites by coherent X-ray diffraction imaging, showing the presence of a strain within the crystal arising from the heterogeneous core-shell structure, which is supported by finite element model calculation and confirmed by fluorescence measurement. The shell is composed of H-ZSM-5 with intrinsic negative thermal expansion whereas the core exhibits a different thermal expansion behaviour due to the presence of organic template residues, which usually remain when the starting materials are insufficiently calcined. Engineering such strain effects could have a major impact on the design of future catalysts.

Effect of metal doping, doped structure, and annealing under argon on the properties of 30 nm thick ultrathin hematite photoanodes.

The doping of the whole hematite layer with W (9.4%) and the additional doping of the bottom half of the W-doped hematite layer with Sn (8.6%), and the subsequent annealing under argon at 600 °C give rise to large increases in the Fe(2+) concentration (by >∼200 times), carrier density (Cd, by ∼48 times) and current density (i(d), by ∼8 times at 1.23 V vs. RHE, under 1 sun) with respect to those of bare hematite photoanodes. The measured i(d) (0.9 mA cm(-2)) is the highest among those of the ultrathin hematite photoanodes and the measured Cd (3.8 × 10(22) cm(-3)) is the highest among those ever observed for hematite.

A novel vanadosilicate with hexadeca-coordinated Cs(+) ions as a highly effective Cs(+) remover.

The effective removal of (137) Cs(+)  ions from contaminated groundwater and seawater and from radioactive nuclear waste solutions is crucial for public health and for the continuous operation of nuclear power plants. Various (137) Cs(+)  removers have been developed, but more effective (137) Cs(+)  removers are still needed. A novel microporous vanadosilicate with mixed-valence vanadium (V(4+) and V(5+) ) ions is now reported, which shows an excellent ability for Cs(+)  capture and immobilization from groundwater, seawater, and nuclear waste solutions. This material is superior to other known materials in terms of selectivity, capacity, and kinetics, and at very low Cs(+)  concentrations, it was found to be the most effective material for the removal of radioactive Cs(+)  ions under the test conditions. This novel vanadosilicate also contains hexadeca-coordinated Cs(+)  ions, which corresponds to the highest coordination number ever described.

Length-dependent change of optical, magnetic, and vibrational properties of vanadate (V(IV)O3(2-)) quantum wire embedded in AM-6 vanadosilicate.

AM-6 and VSH-1 are vanadosilicates containing VO(3)(2-) quantum wires and oxovanadate [O═VO(4)](2-) quantum dots, respectively. We developed methods to synthesize pure, highly crystalline, monodisperse, and all-V(IV) AM-6 and VSH-1 crystals with sizes between 0.2-0.3 and 10 µm. On the basis of their optical, magnetic susceptibility, vibrational, and electron spin resonance (ESR) properties, we have elucidated the following interesting phenomena. The length of the VO(3)(2-) quantum wire (l) linearly increases as the length along the [110] direction {L([110])} increases. The band gap energy (E(g)) of the VO(3)(2-) quantum wire progressively decreases with increasing l even when it reaches ~210 nm, indicating that the Bohr length (the length at which the quantum confinement effect no longer appears) is longer than 200 nm. The deduced µ(z) and µ(xy) are 0.0005m(e) and 15.7m(e), respectively. Per-V(IV)-ion oscillator strength of the d-d transition increases by 7-9 times and that of CT transition increases by 1.5-1.9 times with increasing l from ~50 to 210 nm (by ~4 times). The longitudinal vibration frequency ν of the VO(3)(2-) quantum wire decreases and the intensity of the vibrational band increases as l increases. The ESR intensity increases while the peak-to-peak width decreases as l increases, indicating that the spin-spin relaxation rate (R(ssr)) decreases as l increases. The magnetic susceptibility χ decreases as l increases, especially at T > 125 K, indicating that the tendency of the d(1) electron spins to orient to the external magnetic field decreases with increasing l.

Increase of third-order nonlinear optical activity of PbS quantum dots in zeolite Y by increasing cation size.

The third-order nonlinear optical (3NLO) activity of PbS quantum dots (QDs) encapsulated in zeolite Y has been expected to depend sensitively on the countercation of the zeolite host. However, ion exchange of the pristine countercation, H(+), with other cations has not been possible because the framework decomposes and the QDs aggregate immediately when the PbS QD-incorporating zeolite Y with H(+) as the countercation is exposed to the atmosphere. We now report that when H(+) is transformed to NH(4)(+), the framework of PbS QD-containing zeolite Y does not undergo decomposition and the PbS QDs do not undergo aggregation to form larger QDs during the aqueous ion exchange of NH(4)(+) with alkali-metal ions (M(A)(+) = Li, Na(+), K(+), Rb(+)). The 3NLO activity of the M(A)(+)-exchanged PbS QD-incorporating zeolite Y film increases with increasing size of M(A)(+). The stabilization of the surface-bound exciton by the electron-rich framework oxide and electron-poor cation is proposed to be responsible for the increase. This is the first example of a method for systematically increasing the 3NLO activity of QDs dispersed in a dielectric matrix by systematically changing its properties. These results will serve as a guideline for future research and also promote applications of QD-incorporating zeolites in various fields.

Fluorescence characteristics of isolated dye molecules within silicalite-1 channels.

Fluorescence characteristics of hemicyanine dye molecules isolated from neighboring molecules and strongly restricted inside nanosized pores of zeolite (silicalite-1) crystal were investigated. For samples in which the molecules were sufficiently far away from the others, the fluorescence decay lifetime of the molecules was about 2.2 ns. As the intermolecular distance was reduced, the steady-state fluorescence peak shifted toward the longer wavelength and the fluorescence efficiency decreased markedly. The fluorescence decay lifetime also decreased to 0.8 ns for a sample with the smallest intermolecular distance of 2.1 nm. These results were explained in terms of a dipole-dipole interaction between pairs of dye molecules. From the relation between the intermolecular distances and the fluorescence decay lifetimes of the molecules, the radius of energy transfer of hemicyanine donor-acceptor pair in zeolite matrix was determined to be 2.2 nm, in fair agreement with the calculated Förster radius between dye molecules of the same species.

Increase in Photocurrent Density of WO3 Photoanode by Placing a Layer of an Ordered Array of Mesoporous WO3 Micropillars on Top of a WO3 Sheet Layer.

A facile stamping method was developed to assemble ordered arrays of mesoporous WO3 micropillars with uniform sizes, shapes, and lengths on F-doped tin oxide glass. Using this method, a series of WO3 heterostructural bilayer photoanodes consisting of an array of m-µm long ordered mesoporous WO3 micropillars at the top and the n-µm thick mesoporous WO3 plain sheet layer at the bottom (denoted as m/n) were prepared. Among them 2.5/7.5 displayed a steady state photocurrent density of 3.6 mA cm-2 at 1.23 V (vs RHE) under AM 1.5 (1 Sun), which is much higher than that of the plain 10-µm thick WO3 sheet (2.5 mA cm-2). This phenomenon occurs owing to the following six benefits: increases in charge carrier density, number of photogenerated electron, charge collection rate, thermodynamic feasibility for the vectorial charge transport from the outermost layer of the photoanode to the inner layer, the surface hydrophilicity, and the decrease in charge transfer resistance.

Effect of water on the behavior of semiconductor quantum dots in zeolite Y: aggregation with framework destruction with H-Y and disaggregation with framework preservation for NH4-Y.

Treatment of dry M(2+)-exchanged zeolite Y (M(2+) = Cd(2+), Mn(2+), and Zn(2+)) with dry H(2)S leads to the formation of isolated, ligand-free, subnanometer MS quantum dots (QDs) in zeolite Y with no framework destruction and with H(+) as the countercation. Treatment of the dry H(+)/CdS QD-incorporating zeolites Y with dry NH(3) leads to the neutralization of H(+) to NH(4)(+). During this process, the framework structure remains intact. However, small amounts of interconnected CdS QDs were formed within the zeolite Y by coalition of isolated CdS QDs at the windows. With H(+) as the countercation, isolated CdS QDs rapidly aggregate into interconnected and mesosized QDs with accompanying destruction of ∼50% of sodalite cages leading to the framework rupture. With NH(4)(+) as the countercation, however, the isolated QDs and zeolite framework remain intact even after exposure to the moist air for 4 weeks. Interestingly, the interconnected QDs that were formed during neutralization of H(+) with NH(3) disintegrate into isolated QDs in the air. Similar results were obtained from ZnS and MnS QDs generated in zeolite Y. Thus, ligand-free, naked, subnanometer QDs can now be safely preserved within zeolite pores under the ambient conditions for long periods of time. This finding will expedite the generation and dispersion of various QDs in zeolite pores, their physicochemical studies, and applications.

Photovoltaic effects of CdS and PbS quantum dots encapsulated in zeolite Y.

Zeolite Y films (0.35-2.5 µm), into which CdS and PbS quantum dots (QDs) were loaded, were grown on ITO glass. The CdS QD-loaded zeolite Y films showed a photovoltaic effect in the electrolyte solution consisting of Na(2)S (1 M) and NaOH (0.1 M) with Pt-coated F-doped tin oxide glass as the counter electrode. In contrast, the PbS QD-loaded zeolite Y films exhibited a negligible PV effect. This contrasting behavior was proposed to arise from the large difference in driving force for the electron transfer from S(2-) in the solution to the hole in the valence band of QDs, with the former being much larger (~2 eV) than the latter (~1 eV). In the case of CdS QD-loaded zeolite Y with a loaded amount of CdS of 6.3 per unit cell, the short circuit current, open circuit voltage, fill factor, and efficiency were 0.3 mA cm(-2), 423 V, 28, and 0.1%, respectively, under the AM 1.5, 100 mW cm(-2) condition. This cell was stable for more than 18 days of continuous measurements. A large (3-fold) increase in overall efficiency was observed when PbS QD-loaded zeolite Y on ITO glass was used as the counter electrode. This phenomenon suggests that the uphill electron transfer from ITO glass to S in the solution is facilitated by the photoassisted pumping of the potential energy of the electron in ITO glass to the level that is higher than the reduction potential of S by PbS QDs. Under this condition, the incident-photon-to-current conversion efficiency (IPCE) value at 398 nm was 42% and the absorbed-photon-to-current conversion efficiency (APCE) value at 405 nm was 82%. The electrolyte-mediated interdot charge transport within zeolite films is concluded to be responsible for the overall current flow.

Strain Development of Selective Adsorption of Hydrocarbons in a Cu-ZSM-5 Crystal.

Zeolites are 3D aluminosilicate materials having subnanometer pore channels. The Lewis basic pores have charge-balancing cations, easily tuned to metallic ions as more chemically active sites. Among the ion-exchanged zeolites, Cu2+ ion-exchanged ZSM-5 (Cu-ZSM-5) is one of the most active zeolites with chemical interactions of Lewis basic compounds. Even though the chemical interactions of hydrocarbons with Cu2+ sites in Cu-ZSM-5 have been tremendously studied in the category of zeolite catalysts, it is not yet thoroughly investigated how such interactions affect the structural lattice of the zeolite. Hydrocarbons with different chemical properties and their relative size can induce lattice strain by different chemical adsorption effects on the Cu2+ sites. In this work, we investigate the internal deformation of the Cu-ZSM-5 crystal using Bragg coherent X-ray diffraction imaging during the adsorption of four hydrocarbons depending on the alkyl chain length, the existence of a double bond in the molecule, linear structure versus benzene ring structure, and so forth. In the three-carbon system (propane and propene), relatively weak chemical adsorption occurred at room temperature and 100 °C, whereas strong adsorption was observed over 150 °C. For the six-carbon system (n-hexane and benzene), strong strains evolved in the crystal by active chemical adsorption from 150 °C. The observations suggest that propene and propane adsorb at the Cu2+ sites from the outer shell to the center with increasing temperature. In comparison, n-hexane and benzene adsorb at both parts at the same temperature. The results provide the internal structural information for the lattice with the chemical interactions of hydrocarbons in the Cu-ZSM-5 zeolite and help to understand zeolite-based chemisorption or catalysis research.

Linkage-nondestructive surface migration of zeolite microcrystals during monolayer assembly on glass through ionic linkages.

Monolayers of zeolite microcrystals were prepared on glass plates with three different types of linkage between zeolite crystals and the substrate, namely, (a) covalent, (b) ionic, and (c) poly electrolyte-mediated ionic linkages using sonication with stacking (SS) as the method. The required periods for the coverage to reach 100% were 2, 3, and 7 min, respectively, upon changing the linkage from (a) to (b) and to (c), respectively, indicating that the surface migration becomes slower as the binding strength increases. The coverage, binding strength, and degree of close packing gradually decreased with reaction time with (a) as the linkage while those with (b) and (c) as the linkages remain essentially unaltered. The results indicate that the surface migration of crystals undergo linkage-destructively when crystals were attached to the substrates through covalent linkages and linkage-nondestructively when crystals were attached to the substrates through ionic linkages.

Control of mode of crystal networking during monolayer assembly of microcrystals on water.

A series of hydrocarbon (HC)-coated cubic zeolite microcrystals (1.7 microm) was prepared. The HCs were n-octyl, n-dodecyl, methyl n-undecanoate, n-octadecyl, and n-heptadecafluorodecyl. The measured water contact angles (theta) of the corresponding HC-coated glass plates were 64, 77, 82, 102, and 105 degrees, respectively, indicating that the hydrophobicity of the surface-tethered hydrophobic chain (HC) increased in the above order. The HC-coated zeolite microcrystals readily formed closely packed monolayers at the air-water interface through interdigitation of surface-tethered HCs, and on glass plates after transferring onto glass plates by dip coating. Interestingly, while the mode of networking was face-to-face (FTF) contacting with n-octyl or n-dodecyl (theta < or =77 degrees) as HC, it changed to edge-to-edge (ETE) contacting mode with n-octadecyl or n-heptadecafluorodecyl (theta > or = 102 degrees) as HC. With methyl n-undecanoate (theta = 82 degrees) as HC, both modes appeared in the monolayers, with about equal populations. The resulting monolayers of cubic zeolite microcrystals with their three-fold axes oriented perpendicular to substrates would be useful for application of the zeolite monolayers for advanced materials.

Time-resolved in situ visualization of the structural response of zeolites during catalysis.

Zeolites are three-dimensional aluminosilicates having unique properties from the size and connectivity of their sub-nanometer pores, the Si/Al ratio of the anionic framework, and the charge-balancing cations. The inhomogeneous distribution of the cations affects their catalytic performances because it influences the intra-crystalline diffusion rates of the reactants and products. However, the structural deformation regarding inhomogeneous active regions during the catalysis is not yet observed by conventional analytical tools. Here we employ in situ X-ray free electron laser-based time-resolved coherent X-ray diffraction imaging to investigate the internal deformations originating from the inhomogeneous Cu ion distributions in Cu-exchanged ZSM-5 zeolite crystals during the deoxygenation of nitrogen oxides with propene. We show that the interactions between the reactants and the active sites lead to an unusual strain distribution, confirmed by density functional theory simulations. These observations provide insights into the role of structural inhomogeneity in zeolites during catalysis and will assist the future design of zeolites for their applications.

Facile organization of colloidal particles into large, perfect one- and two-dimensional arrays by dry manual assembly on patterned substrates.

The ability to rapidly and reproducibly assemble colloidal particles into large (>mm) one- (1D) and two-dimensional (2D) single crystals with perfect control of the particle networking pattern would open a new world rich with high quality novel materials, technologies, and sciences. However, current methods rely on self-assembly of colloidal particles in solution (wet self-assembly), which intrinsically makes the assembly of the colloidal particles into defect-free large 1D and 2D single crystals difficult. We now demonstrate a new paradigm of colloidal particle organization into 1D and 2D single crystals, a process we call 'dry manual assembly on nanolithographically patterned substrates', which enables facile and rapid organization of colloidal particles in dry states into 1D and 2D single crystals in the centimeter or larger scales with a well-defined particle networking pattern. We believe that this novel methodology will serve as a key to open a new era of particle organization.

New insights into ETS-10 and titanate quantum wire: a comprehensive characterization.

The titanate quantum wires in ETS-10 crystals remain intact during ion exchange of the pristine cations (Na(+)(0.47) + K(+)(0.53)) with M(n+) ions (M(n+) = Na(+), K(+), Mg(2+), Ca(2+), Sr(2+), Ba(2+), Pb(2+), Cd(2+), Zn(2+)) and during reverse exchange of the newly exchanged cations with Na(+). The binding energies of O(1s) and Ti(2p) decrease as the electronegativity of the cation decreases, and they are inversely proportional to the negative partial charge of the framework oxygen [-delta(O(f))]. At least five different oxygen species were identified, and their binding energies (526.1-531.9 eV) indicate that the titanate-forming oxides are much more basic than those of aluminosilicate zeolites (530.2-533.3 eV), which explains the vulnerability of the quantum wire to acids and oxidants. The chemical shifts of the five NMR-spectroscopically nonequivalent Si sites, delta(I(A)), delta(I(B)), delta(II(A)), delta(II(B)), and delta(III), shift downfield as -delta(O(f)) increases, with slopes of 2.5, 18.6, 133.5, 216.3, and 93.8 ppm/[-delta(O(f))], respectively. The nonuniform responses of the chemical shifts to -delta(O(f)) arise from the phenomenon that the cations in the 12-membered-ring channels shift to the interiors of the cages surrounded by four seven-membered-ring windows. On the basis of the above, we assign delta(I(A)), delta(I(B)), delta(II(A)), and delta(II(B)) to the chemical shifts arising from Si(12,12), Si(12,7), Si(7,12), and Si(7,7) atoms, respectively. The frequency of the longitudinal stretching vibration of the titanate quantum wire increases linearly and the bandwidth decreases nonlinearly with increasing -delta(O(f)), indicating that the titanate quantum wire resembles a metallic carbon nanotube. As the degree of hydration increases, the vibrational frequency shifts linearly to higher frequencies while the bandwidth decreases. We identified another normal mode of vibration of the quantum wire, which vibrates in the region of 274-280 cm(-1). In the dehydrated state, the band-gap energy and the first absorption maximum shift to lower energies as -delta(O(f)) increases, indicating the oxide-to-titanium(IV) charge-transfer nature of the transitions.

Fluorescence properties of hemicyanine in the nanoporous materials with varying pore sizes.

Hemicyanine dye molecules were put into the nanoporous materials (silicalite-1, zeolite-beta, and MCM-41) with different pore sizes. Fluorescence anisotropy measured from these systems indicated that the incorporated dye molecules were well-aligned along the straight channel of the zeolite pores, except for dye molecules in the largest pores of MCM-41. The fluorescence decay lifetimes were 2.1, 1.7, and 1.1 ns, for the dyes in silicalite-1, zeolite-beta, and MCM-41, respectively. Significant increase in the fluorescence intensity and the fluorescence decay lifetime was observed with the decrease of the pore size. This was due to intramolecular rotational motion of the dye molecules more hindered in smaller pores, demonstrating the fluorescence properties of the dye molecule can be controlled at will by the choice of zeolite matrix.

Synthesis of diamond-shape titanate molecular sheets with different sizes and realization of quantum confinement effect during dimensionality reduction from two to zero.

Synthesis of semiconductor nanoparticles with uniform shapes, sizes, and compositions in series with a gradual size reduction has not been achieved for two-dimensional molecular sheets. We report a large-scale (>2.6 g) synthesis of 0.75-nm-thick diamond-shape lepidocrocite-type titanate molecular sheets with the sizes decreasing from (27.3, 19.1) to (7.7, 5.5), where the numbers in parentheses represent the long and short diagonal lengths, respectively, in nm. This is the first example of synthesizing semiconductor nanoparticles in series with the dimensionality reduction from two to zero, without coating the surfaces with surface-passivating ligands. The titanate molecular sheets showed three exciton-absorption bands in the 4.0-6.5 eV region, the absorption energies of which increased with decreasing the area. Contrary to the common belief, the per-unit cell oscillator strengths gradually increased with increasing area and the per-particle oscillator strengths increased in proportion to the area. The average reduced exciton masses along the two diagonal axes were 0.10 and 0.11 m e, respectively, which were much smaller than those of bulk titanates (by 60-130 times). The estimated average Bohr radii along the two-diagonal axes were 4.8 and 4.3 nm, respectively.